Compositions and methods for reducing interaction between abrasive particles and a cleaning brush

ABSTRACT

Described are methods for removing abrasive particles from a polymeric surface, such as from a polymeric surface of a cleaning brush used in a post chemical-mechanical processing cleaning step, as well as related cleaning solutions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 16/172,139, filed Oct. 26, 2018, which claims the benefit under35 USC 119 of U.S. Provisional Patent Application No. 62/594,139, filedDec. 4, 2017, the disclosures of which are hereby incorporated herein byreference in their entirety for all purposes.

FIELD OF THE INVENTION

The invention relates to methods for removing abrasive particles from apolymeric surface, such as from a polymeric surface of a cleaning brushused in a post chemical-mechanical processing cleaning step.

BACKGROUND

In areas of technology that relate to the production (fabrication) ofmicroelectronic devices, which include integrated circuits, opticaldevices, memory devices, magneto-electric components, and othermicro-devices or microdevice components used in electronic, memory,optical, and similar applications, a microelectronic device is preparedby steps that include precisely removing material from a substratesurface. Methods used to prepare certain devices may include a series ofsteps of depositing and selectively removing different materials at asurface of a substrate. A material applied during processing may be aconductive material such as a metal, a semiconductor material such as asilicon-based material (e.g., silicon oxide), a dielectric layer, or apolymeric material, among others. The materials may be selectivelyapplied and selectively removed, at the surface, in a manner that buildslayers of microelectronic structures on the substrate. Removal ofmaterial may be done by selective chemical means, by abrasive means, ora combination of these.

In preparing these devices, a processing step that planarizes, flattens,or polishes a substrate surface by abrasive means is commonly used.Between steps of selectively applying and removing materials at asurface, the surface is processed to provide a highly refined (e.g.,flat, planarized, or polished) level of finish. The standard techniquefor such processing is chemical-mechanical processing (CMP). Inchemical-mechanical processing, a surface of a substrate is contactedwith an abrasive slurry and with a CMP pad, with relative movementbetween the pad and the surface. The slurry contains liquid carrier(water or organic solvent), dissolved chemicals (i.e., organic chemicalmaterials), and dispersed abrasive particles. (The surface willtypically include particulate by-products such as various types of metaloxides, present from previous processing steps.) The combination of theingredients of the slurry and the movement between the pad and thesubstrate surface are effective to remove material from the substratesurface and to provide a planarized or polished surface for furtherprocessing.

Following a CMP step, various materials that are part of the slurry, aswell as materials that have been removed from the substrate surface,remain at the surface of the substrate as chemical or abrasive residue.Chemical residue may be a residual chemical ingredient that is presentat the substrate surface after a CMP process, and that is a chemicalmaterial present originally in the CMP slurry or a derivative (e.g.,reaction product) thereof. Abrasive particle residue refers to abrasiveparticles that were originally present in the CMP slurry and that remainat the substrate surface at an end of a CMP step. Other types of residuecan be a combination of abrasive particles and chemical residue, such asagglomerated, coagulated, or precipitated, organic and abrasive particlematerials.

Significant efforts are made during processing of microelectronicdevices, e.g., after or between CMP steps, to remove residue from asubstrate surface. Residue in the form of residual abrasive particles,in particular, must be removed from a substrate surface because residualabrasive particles can result in surface defects such as scratches, aswell as device defects in the form of embedded particles that can have anegative impact on downstream processing of the substrate or on thequality of the downstream product. Methods for removing residue,including residual abrasive particles, include cleaning techniquessometimes referred to as “post-CMP cleaning” techniques, methods, orsteps. These involve the use of a cleaning solution applied to a surfaceof a substrate that includes a residue, along with contact by a movingpolymeric brush, to chemically and mechanically remove the residue fromthe surface.

Many varieties of post-CMP cleaning equipment and cleaning solutions arecommercially available. Example apparatus include a cleaning chamberthat contains moving brushes along with a system to dispense cleaningsolution onto a substrate surface within the cleaning chamber, and toprovide motion and contact between the substrate and the brushes. Thechamber usually can be heated to facilitate cleaning. In use, thecleaning solution is applied to the substrate surface, and the surfaceis brought into contact with the moving brushes, to remove residue.While examples of these types of apparatus and methods are known, arecommercially useful, and may be capable of efficient and effectivepost-CMP cleaning of various substrates, there is always a need toimprove on existing technologies and to develop new and even moreeffective cleaning solutions and cleaning methods for removing residuefrom CMP substrate surfaces.

SUMMARY

The invention relates to methods and composition useful for removingabrasive particles from a polymeric surface, such as from a polymericsurface of a cleaning brush used in a post chemical-mechanicalprocessing cleaning step, as well as related cleaning solutions. TheApplicant has determined that abrasive particles, especially thosehaving hydrogen bonding groups at surfaces of the particles, a positivecharge (positive zeta potential) in a cleaning solution used in apost-CMP cleaning step, or both, can be attracted to hydrogen bondinggroups present at a polymeric surface of a cleaning brush during apost-CMP cleaning step.

During processing of microelectronic devices substrates, prior to apost-CMP cleaning step, a microelectronic device substrate can haveresidue at its surface, such as residual abrasive particles. During thepost-CMP cleaning step those abrasive particles are removed (at least inlarge part) from the substrate surface and become dispersed in cleaningsolution used with the post-CMP cleaning step. While in the cleaningsolution, especially at a condition of a low pH (e.g., below 6 or 7),the dispersed abrasive particles can exhibit a positive charge, i.e., apositive zeta potential. Surfaces of the abrasive particles can alsoinclude hydrogen bonding groups such as (—OH) groups, e.g., a silanol(—SiOH) in the case of silica particles. The surfaces of the positivelycharged particles having hydrogen bonding groups thereon areelectrostatically attracted to and can form hydrogen bonds with hydrogenbonding groups present at a surface of a polymeric brush used in thepost-CMP cleaning step. The abrasive particles can become attracted toand can accumulate at the surface of the polymeric brushes, and canmaintain an attraction to the surface by hydrogen bonding, particularlyin the presence of a cleaning solution that has a low pH. One potentialresult of the presence and accumulation of abrasive particles at asurface of a cleaning brush during a post-CMP cleaning step can be thepresence of brushmarks following the post-CMP cleaning step.

As used herein, a “hydrogen bonding group,” e.g., as a feature of aparticle removal agent, a polymeric surface of a brush, or an abrasiveparticle, is a polar compound or a polar group that is capable ofinteracting with another hydrogen bonding group to form of hydrogenbond. Examples include a group that includes a hydrogen (H) atomcovalently bound to a highly electronegative atom such as nitrogen (N),oxygen (O), sulfur (S), or fluorine (F). Certain specific hydrogenbonding groups include: a carboxylic acid, an amino group, an alcohol, aphosphine, phosphate, phosphonate, an alkanolamine, a carbamide, a urea,urethane, an ester, a betaine, a silanol group, or a sulfur-containinggroup.

According to presently-described cleaning solutions and methods of theiruse, a cleaning solution includes a dissolved chemical ingredient,referred to as a particle removal agent, that is effective to preventthe formation of hydrogen bonds between positively-charged abrasiveparticles in a cleaning slurry and a polymeric brush surface, during apost-CMP cleaning step; to inhibit or reduce the formation of hydrogenbonds between such abrasive particles and a polymeric brush surfaceduring a post-CMP cleaning step; or to remove such abrasive particlesthat are attracted to and have formed hydrogen bonds with a surface of apolymeric brush (either during a post-CMP cleaning step, or in aseparate step of cleaning the brushes in the absence of a substrate).

In one aspect the invention relates to a method of removing abrasiveparticles from a post-chemical-mechanical-processing (post-CMP) cleaningbrush. The method includes: providing a post-CMP cleaning brush having apolymeric surface and having abrasive particle residue at the polymericsurface; and providing a cleaning solution having a pH below 7. Thecleaning solution contains: cleaning agent, and particle removal agent.The method also includes removing abrasive particle residue from thepolymeric surface by contacting the polymeric surface with the cleaningsolution.

In another aspect the invention relates to a method ofpost-chemical-mechanical-processing (post-CMP) cleaning of a substrate.The method includes: providing a post-CMP cleaning brush having apolymeric surface; and providing a cleaning solution that includes:cleaning agent, and particle removal agent. The method also includesproviding a substrate that includes a surface, with residue at thesubstrate surface, the residue including abrasive particles, andremoving residue from the substrate surface by exposing the substratesurface and the polymeric surface to the cleaning solution whilecontacting the substrate surface with the polymeric surface and whilemoving the substrate surface relative to the polymeric surface.

In another aspect the invention relates to a cleaning solutionconcentrate useful for cleaning a substrate in apost-chemical-mechanical processing step. The cleaning solutionconcentrate includes cleaning agent, and at least 0.1 weight percentparticle removal agent that includes a hydrogen bonding group.

SUMMARY OF THE FIGURES

FIG. 1 shows performance data of wafers cleaned with specificallydescried methods and materials.

FIG. 2 shows a proposed mechanism of brush imprint formation.

FIG. 3 shows FTIR spectrum data of a brush having silica at a surface,as described.

FIG. 4 shows FTIR spectra data of a brush having silica at a surface,with different cleaning materials.

FIGS. 5 and 6 show data derived from the use of various cleaningsolutions as described.

DETAILED DESCRIPTION

The present description relates, in different aspects, to: methods ofremoving abrasive particles from a surface of a cleaning brush used in apost-CMP cleaning step (the method being incorporated into a post-CMPcleaning process, or being a separate process or step that removesabrasive particle from the brush); methods of preventing accumulation ofabrasive particles from surfaces of a cleaning brush during a post-CMPcleaning process for removing residue from a substrate surface; and tocleaning solutions effective in these methods, wherein the cleaningsolution contains particle removal agent.

During chemical-mechanical processing, i.e., CMP or “CMP processing,” asubstrate is processed to planarize or polish a surface of the substrateby controlled removal of minute amounts of material from the surface.The microelectronic device substrate, i.e., “substrate” for short, canbe any type of microelectronic device or a precursor thereof, meaning adevice or precursor that is or contains any of an integrated circuit,optical device, solid state memory device, hard disk memory device,magneto-electric component, or another type of microdevice ormicrodevice component that is useful in an electronic, memory, optical,or similar application and that is prepared by a fabrication processthat includes one or more steps of chemical-mechanical-processing asurface of the substrate, often with multiple steps of depositing andselectively removing combinations of materials at the surface of asubstrate.

A substrate for use in methods as described can include any material orcombination of materials, at a surface, that are part of an in-processmicroelectronic device, including: semiconducting materials (e.g.,silicon), ceramics (e.g., silicon carbide, silicon nitride), glassmaterials, electrically conductive materials (e.g., metals and metalalloys), electrically insulating (dielectric) materials, barriermaterials, and the like. Electrically conductive materials may be metalsor alloys of metals that include copper, tungsten, silver, aluminum, andcobalt, as well as others and alloys thereof. Electrically insulatingdielectric materials may be any of a variety of presently-known orto-be-developed insulating, low-k, or ultra-low-k dielectric materialsincluding various forms of doped or porous silicon dioxide, thermaloxide, TEOS, to name a few examples. Examples of materials of asubstrate that may be present as a barrier layer include: tantalum,tantalum nitride, titanium nitride, cobalt, nickel, manganese,ruthenium, ruthenium-nitride, ruthenium-carbide, or ruthenium tungstennitride.

A CMP process involves applying a slurry to a surface of the substrateand contacting the slurry and the substrate with a pad (i.e., a “CMPpad” or a “CMP polishing pad”), with movement between the pad and thesurface. The slurry contains abrasive particles designed to causefrictional (mechanical) removal of material from the surface of thesubstrate. The slurry will typically also contain various chemicalingredients dissolved therein that can be effective to control (increaseor decrease) the rate of removal of certain materials from the substratesurface; to provide desired selectivity of removal of differentmaterials; to reduce the presence of defects and the amount of residueat the substrate surface during and after the CMP step; or to otherwisefacilitate an improved or desired result relating to the efficiency ofthe CMP process or the quality of the substrate at the end of the CMPprocess.

Example slurries (“CMP slurries”) include liquid carrier that can bemostly water (preferably, deionized water) in which the chemicalmaterials and abrasive particles are dissolved or dispersed. Thechemical materials of the slurry can be selected to achieve desiredremoval rates, selectivity of removal, and final topography (e.g.,smoothness, waviness, etc.) of the finished substrate surface. Thespecific types and amounts of chemical materials in a particular slurrycan depend on various factors, such as the type or types of materialspresent at the substrate surface, CMP processing conditions, the type ofCMP pad used in the CMP step, the type or types of abrasive particles ofthe slurry, etc. Example chemical ingredients include chemical materialssuch as those that can function as a solvent, surfactant, catalyst,stabilizer, oxidizer, organic inhibitor (to control a removal rate),chelating agent, among others. Other possible chemical materials includepH adjusting agents (base, acid), a corrosion inhibitor, and biocide (asa preservative).

The abrasive particles can have size and composition features to effectthe efficient, optionally selective, and uniform removal of specificmaterials from the substrate surface. Example abrasive particles may bemade of or contain alumina, ceria, ceria oxide, zirconium, zirconiumoxide, silica (various forms), titanium dioxide, zirconia, diamonds,silicon carbide, or other metal, ceramic, or metal oxide materials.Various sizes, size distributions, particle shapes, and other physicalor mechanical properties of these types of abrasive particles areavailable and can be selected for use with various substrates or CMPprocesses. An amount of abrasive particles in a slurry can also beselected based on similar factors relating to the type of substratebeing processed and features of the CMP process.

For use in processing different types of substrates, the abrasiveparticles may be selected to exhibit an electrostatic charge, which maybe positive or negative, when the particles are dispersed in the CMPslurry. The strength of a charge of a dispersed abrasive particle iscommonly referred to as the “zeta potential” (or the electrokineticpotential) of the particle, which refers to the electrical potentialdifference between the electrical charge of the ions surrounding theparticle and the electrical charge of the bulk liquid of the slurry(e.g., the liquid carrier and any other components dissolved therein).The zeta potential of a dispersed particle is typically dependent on thepH of the liquid medium within which the particle is dispersed. For agiven slurry or other liquid medium, the pH at which the zeta potentialof a charged abrasive particle is zero is referred to as the isoelectricpoint. As the pH of a solution that contains the dispersed abrasiveparticles is increased or decreased away from the isoelectric point, thesurface charge (and hence the zeta potential) is correspondinglydecreased or increased (to more highly negative or more highly positivezeta potential values).

During steps of CMP processing, various materials are present in theslurry, including the dissolved and dispersed (e.g., suspended)ingredients of the slurry, as well as other dissolved or dispersedmaterials that are generated during the CMP process, such as by beingremoved from the substrate surface. Additionally present may bederivatives, reaction products, agglomerates, coagulates, andprecipitates of any of these. Any such material present in the slurryduring a CMP processing step can potentially become a residue thatremains at a surface of the substrate at the end of the CMP processingstep. Thus, residue at a substrate surface after a CMP step mightinclude: dissolved chemical material or solid abrasive particles thatare originally present in a CMP slurry; materials that become removedfrom a substrate surface during processing (e.g., a metal ion) or thatare generated during processing by reaction or chemical modification(e.g., oxidization or reduction) of a chemical material of the slurry;or combinations of these, including precipitates, agglomerates, andcoagulates.

As is known generally, various post-CMP cleaning steps are useful forremoving residues that are present on a surface of a microelectronicdevice following a CMP processing step. These cleaning steps can andgenerally do involve the use of specialized post-CMP cleaning equipment,which may include a cleaning apparatus that includes a cleaning chamberwherein a cleaning solution is delivered to a surface of a substrate, incombination with the application of moving polymeric brushes to thesurface to mechanically remove the residue from the substrate surface.The conditions and cleaning time (meaning the amount of time thesubstrate surface is exposed to the moving brush and the cleaningsolution) can be selected based on factors such as the type ofsubstrate, the type of brushes, the types and amounts of residue at thesurface, the type of cleaning solution, etc.

A variety of post-CMP cleaning tools that involve the use of polymericbrushes are known and are commercially available. These apparatusgenerally include a cleaning chamber that includes a moveable cleaningbrush (typically multiple cleaning brushes); a source of cleaningsolution; a source of heat; and systems, mechanism, devices, including acontrol system, adapted to place the cleaning solution in contact withthe substrate, cleaning solution, and moving brushes, at conditions(time and temperature) effective to cause mechanical removal of residuefrom the surface. Companies that sell this type of equipment include:Entegris, Inc.; AION; Ceiba Technologies, Inc.; Rippey Corp.; AppliedMaterials; Ebarra, among others.

A polymeric cleaning brush for use in a post-CMP cleaning apparatus andmethod according to the present description includes a polymeric surfacethat contains hydrogen bonding groups, e.g., hydroxy groups (—OH)attached to a polymeric backbone. Cleaning brushes that include apolymeric surface and that are useful in post-CMP cleaning processes arewell known. Examples of cleaning brushes that contain a polymericsurface having hydroxy groups attached to a polymeric backbone includebrushes made of polymer that is derived, at least in part, from vinylalcohol, i.e., polymer that is either a homopolymer or copolymer ofvinyl alcohol, such polymers (co-polymers and homopolymers) commonlyreferred to as polyvinylalcohol (a.k.a. “PVOH” or “PVA”).

Examples of cleaning brushes used in post-CMP cleaning steps aredescribed, for example, in United States patent application20013/0048018, the entirety of which is incorporated herein byreference. As described therein, a cleaning brush may be prepared by useof polyvinyl alcohol as a starting material, which may be then processedto form a polyvinyl acetal elastic material. The polyvinyl alcoholstarting material may be processed with an aldehyde, e.g., formaldehyde,to produce a polyvinyl alcohol brush material. Other polymers, eitherinstead of or in addition to polyvinyl alcohol, may be useful aspolymeric materials for a brush and may include hydrogen bonding groups.Examples of such other polymers include polymeric and co-polymericnylon, polyurethane, and combinations of these, which can be formed intoa cleaning brush suitable for cleaning residue from a substrate asdescribed herein, in a commercial post-CMP cleaning process.

Example brushes include a cylindrical polymeric (as described) foambrush with a first end and a second end, and an outer surface with aplurality of nodules extending from a base surface of the brush. Thenodules are located along the length of the brush, between the first andsecond ends, and are separated from each other by gaps or openings. Thenodules may have any shape and often include a circular top surface anda surface height that extends from a base of the brush to the topsurface of the nodule. When the brush is rotated about an axis extendingbetween the first and second ends, the outer cylindrical surface of thebrush rotates, as do the nodules on the surface. A surface of thesubstrate, having cleaning solution applied thereto, can be brought intocontact with the moving surface of the brush and the brush nodules toallow the nodules to contact the surface to facilitate removal ofresidue from the surface.

The timing and conditions of the cleaning process should be effective toremove a large portion of a total amount of residue (e.g., as measuredby abrasive particle residue) from the substrate surface, in anefficient manner. For example, by use of a typical post-CMP cleaningapparatus and method, a cleaning solution may be contacted with thesubstrate surface, and the surface will be contacted with the polymericbrushes (with movement between the substrate surface and the brushes)for a time sufficient to remove a high percentage of residue (e.g.,abrasive particle residue) present at the surface before the cleaningstep. Desirably, a useful post-CMP cleaning step can result in removalof at least 85 percent of the residue (e.g., abrasive particle residue)present on the substrate surface prior to residue removal, morepreferably at least 90 percent, even more preferably at least 95percent, and most preferred at least 99 percent. Methods and equipmentuseful to measure an amount of residue (e.g., particle residue)remaining at a surface of a substrate are well known and arecommercially available.

To achieve such a level of residue removal, example cleaning times ofthe substrate by the cleaning apparatus may be in a range from about 1second to about 20 minutes, preferably about 5 seconds to 10 minutes,e.g., in a range from about 15 seconds to about 5 minutes, attemperature in a range of from about 20 degrees Celsius to about 90degrees Celsius, preferably about 20 to about 50 degrees Celsius.Processing times in these ranges of time and temperature areillustrative, and any other suitable time and temperature conditions maybe used if effective to at least partially clean post-CMP residue from asurface of a substrate.

According to the present invention, the Applicant has now specificallyidentified that abrasive particles, especially those having hydrogenbonding groups at surfaces of the particles, a positive charge (positivezeta potential) in a cleaning solution used in a post-CMP cleaning step,or both, can be attracted to hydrogen bonding groups present at apolymeric surface of a cleaning brush during a post-CMP cleaning step.

Before a post-CMP cleaning step, a microelectronic device substrate canhave abrasive particle residue at its surface. During the cleaning stepthose abrasive particles are removed (at least in large part) from thesubstrate surface and become dispersed in cleaning solution used withthe post-CMP cleaning step. While in the cleaning solution, especiallyat a condition of a low pH (e.g., below 6 or 7), the dispersed abrasiveparticles can exhibit a positive charge, i.e., a positive zetapotential. Surfaces of the abrasive particles can also include hydrogenbonding groups such as (—OH) groups, e.g., a silanol (—SiOH) in the caseof silica particles. The surfaces of the positively charged particleshaving hydrogen bonding groups thereon are electrostatically attractedto and can form hydrogen bonds with hydrogen bonding groups present at asurface of a polymeric brush used in the post-CMP cleaning step. Theabrasive particles can become attracted to and can accumulate at thesurface of the polymeric brushes, and can maintain an attraction to thesurface by hydrogen bonding, particularly in the presence of a cleaningsolution that has a low pH.

One potential result of the presence and accumulation of abrasiveparticles at a surface of a cleaning brush during a post-CMP cleaningstep can be the presence of brushmarks following the post-CMP cleaningstep. Brushmarks (or “brush imprints”) are a visible pattern of residualabrasive particles that are present on a substrate surface after apost-CMP cleaning step. The pattern can include a shape or feature(e.g., dimension) that matches a shape or feature of a surface of acleaning brush used to clean the substrate surface, such as a circularsurface of a cleaning brush nodule. Examples of brushmark patternsformed by residual abrasive particles include circular marks that matcha shape and size of a nodule, as well as a line pattern that is adistinct line formed from residual abrasive particles, with the lengthof the line corresponding to a diameter of a circular brush nodule. Thebrushmarks can be made of and formed by a pattern of abrasive particles(i.e., abrasive particle residue) that remain on the substrate after astep of post-CMP cleaning. A preferred post-CMP cleaning process of thepresent description can result in a reduced or minimized occurrence of,or preferably an absence of, brushmarks at a surface of a substrateafter the post-CMP cleaning step.

According to example methods of the invention, a post-CMP cleaning stepinvolves an apparatus that includes a scrub brush that has a polymericsurface that contains hydrogen bonding groups. Additionally, thecleaning solution used in the cleaning step can have a low pH, such asbelow about 7, e.g., in a range from about 1 up to about 5 or 6, or fromabout 1 or 2 up to about 3, 3.5 or 4. These factors can result in thepresence of positively-charged abrasive particles (having hydrogenbonding groups) in the cleaning solution during a post-CMP cleaningstep, with the positively-charged abrasive particles becoming attractedto hydrogen bonding groups at the brush surface, causing thepositively-charged abrasive particles to be attracted to the polymericbrush surface by hydrogen bonding.

According to Applicant's novel and inventive cleaning solutions andmethods of their use, a cleaning solution includes a dissolved chemicalingredient, referred to as a particle removal agent, that is effective:to prevent the formation of hydrogen bonds between positively-chargedabrasive particles in a cleaning slurry and a polymeric brush surface,during a post-CMP cleaning step; to inhibit or reduce the formation ofhydrogen bonds between such abrasive particles and a polymeric brushsurface during a post-CMP cleaning step; or to remove such abrasiveparticles that are attracted to and have formed hydrogen bonds with asurface of a polymeric brush (either during a post-CMP cleaning step, orin a separate step of cleaning the brushes in the absence of asubstrate).

Accordingly a cleaning solution of the present description includes oris in the form of a solution that includes an aqueous medium (preferablydeionized water) that contains dissolved ingredients that include:particle removal agent, optionally one or more ingredients that functionas cleaning agents (e.g., chelating agent, organic solvent); andoptionally a small or minor amount of other optional adjuvants such asacid, surfactant, biocide, etc.

A particle removal agent is a chemical compound (including oligomers orpolymers) that includes at least one hydrogen bonding group, and thatwhen present in a cleaning solution as described, and in the presence ofpositively-charged abrasive particles and a polymeric surface of acleaning brush, can be effective to associate with: a hydrogen bondinggroup of a polymeric brush surface, a hydrogen bonding group of apositively-charged abrasive particle, or both, in a manner and a degreeto which the particle removal agent will reduce the amount of abrasiveparticles that are present at a surface of a cleaning brush andattracted to the surface of the cleaning brush by hydrogen bonding.

In a cleaning solution that contains dispersed abrasive particles(brought there as residue on a substrate surface) that arepositively-charged, e.g., at low pH, particle removal agent canassociate with hydrogen bonding groups of the positively-chargedparticles in a manner that inhibits or prevents the positively-chargedparticles from becoming attracted to hydrogen bonding groups present ata surface of a polymeric cleaning brush. Additionally, in the presenceof a cleaning brush that includes hydrogen bonding groups, and at lowpH, particle removal agent can also become associated with hydrogenbonding groups that are present at the surface of the cleaning brush ina manner to inhibit or prevent the cleaning brush from attractingpositively-charged abrasive particles that are present in the cleaningsolution. Considered more generally, the particle removal agent canprevent or disrupt hydrogen bonds between a positively charged abrasiveparticle that includes hydrogen bonding groups, and a polymeric surfaceof a cleaning brush that contains hydrogen bonding groups. These effectsand interactions (alone or in combination) between the particle removalagent and the cleaning brush surface, and the particle removal agent andthe positively-charged abrasive particles, all present in a cleaningsolution (e.g., during a post-CMP cleaning step), effectively reduce theamount of interactions between hydrogen bonding groups of the cleaningbrush surface and hydrogen bonding groups of the positively-chargedabrasive particles. A result can be that fewer of the abrasive particleswill be present at the surface of the cleaning brush and associated withsurface by hydrogen bonding.

Accordingly, a cleaning solution of the present invention includes anamount of particle removal agent, the amount and type being effective toreduce the amount (e.g., concentration) of positively-charged abrasiveparticles present at a polymeric surface of a cleaning brush when thecleaning solution is exposed to the cleaning brush in the presence ofsuch abrasive particles, and at a low pH.

Examples of ingredients that may be useful as a particle removal agentas described include organic compounds, polymers, oligomers, etc., thatcontain one or more hydrogen bonding groups (when present in thecleaning solution and at a low pH), and that can be included in acleaning solution to be effective in reducing the presence ofpositively-charged abrasive particles at a surface of a polymericcleaning brush, as described. Example compounds generally includenitrogen-containing compounds; amino acids; mono, di ormulti-carboxylate-containing groups; alcohols (e.g., polyols); acids;among others.

Some specific examples of particle removal agents include non-ionic,anionic, cationic, and zwitterionic small molecules and polymers thatmay behave as a polyelectrolyte at neutral pH. Anionic polymers oranionic polyelectrolytes can be natural, modified natural polymers, orsynthetic polymers. Exemplary natural and modified natural anionicpolymers that can be included in a cleaning solution as describedinclude, but are not limited to: alginic acid (or salts),carboxymethylcellulose, dextran sulfate, poly(galacturonic acid), andsalts thereof. Exemplary synthetic anionic polyelectrolytes include, butare not limited to: homopolymers or copolymers of (meth)acrylic acid (orsalts), poly(acrylic acid), maleic acid (or anhydride), styrene sulfonicacid (or salts), vinyl sulfonic acid (or salts), allyl sulfonic acid (orsalts), acrylamidopropyl sulfonic acid (or salts), and the like, whereinthe salts of the carboxylic acid and sulfonic acids are preferablyneutralized with an ammonium or alkylammonium cation. Preferred cationsof a polyelectrolyte anionic polymer are ammonium cations (NH₄ ⁺),cholinium ⁺N(CH₃)₃(CH₂CH₂OH) and ⁺N(CH₃)₄. Thus, examples of preferredcombined synthetic and natural polyelectrolyte anionic polymers arehomopolymers or copolymers of (meth)acrylic acid, maleic acid (oranhydride), styrene sulfonic acid, vinyl sulfonic acid, allyl sulfonicacid, vinylphosphonic acid, acrylamidopropyl sulfonic acid, alginicacid, carboxymethylcellulose, dextran sulfate, poly(galacturonic acid),and salts thereof.

Cationic polymers and cationic polyelectrolytes can be natural, modifiednatural polymers, or synthetic polymers. Exemplary natural and modifiednatural cationic polymers include, but are not limited to: chitosan,cationic starch, polylysine, and salts thereof. Exemplary cationicsynthetic polyelectrolytes include but are not limited to: homopolymersor copolymers of diallyldimethyl ammonium chloride (DADMAC),diallyldimethyl ammonium bromide, diallyldimethyl ammonium sulfate,diallyldimethyl ammonium phosphates, dimethallyldimethyl ammoniumchloride, diethylallyl dimethyl ammonium chloride, diallyldi(beta-hydroxyethyl) ammonium chloride, diallyl di(beta-ethoxyethyl)ammonium chloride, dimethylaminoethyl (meth)acrylate acid addition saltsand quaternary salts, diethylaminoethyl (meth)acrylate acid additionsalts and quaternary salts, 7-amino-3,7-dimethyloctyl (meth) acrylateacid addition salts and quaternary salts, N,N′-dimethylaminopropylacrylamide acid addition salts and quaternized salts, wherein thequaternary salts include alkyl and benzyl quaternized salts; allylamine,diallylamine, vinylamine (obtained by hydrolysis of vinyl alkylamidepolymers), vinyl pyridine, chitosan, cationic starch, polylysine, andsalts thereof.

Other examples include 2-pyrrolidinone,1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), glycerol, 1,4-butanediol,tetramethylene sulfone (sulfolane), dimethyl sulfone, ethylene glycol,propylene glycol, dipropylene glycol, tetraglyme, diglyme, a glycolether (e.g., diethylene glycol monomethyl ether, triethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, triethylene glycolmonoethyl ether, ethylene glycol monopropyl ether, ethylene glycolmonobutyl ether, diethylene glycol monobutyl ether (DEGBE), triethyleneglycol monobutyl ether (TEGBE), ethylene glycol monohexyl ether (EGHE),diethylene glycol monohexyl ether (DEGHE), ethylene glycol phenyl ether,propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME),tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethylether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether,dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propylether, propylene glycol n-butyl ether (DOWANOL PnB), dipropylene glycoln-butyl ether, tripropylene glycol n-butyl ether, propylene glycolphenyl ether (DOWANOL PPh)), n-ethylpyrrolidone, n-methylpyrrolidone,dimethylformamide, dimethylsulfoxide, ethylene glycol monohexyl ether,diethylene glycol monohexyl ether and combinations thereof.Alternatively, or in addition to, the cleaning additive can includehydroxypropylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxyproplymethyl cellulose, carboxymethylcellulose. sodiumcarboxymethylcellulose (Na CMC), polyvinylpyrrolidone (PVP), any polymermade using the N-vinyl pyrrolidone monomer, polyacrylic acid esters andanalogoues of polyacrylic acid esters, polyaminoacids (e.g.,polyalanine, polyleucine, polyglycine), polyamidohydroxyurethanes,polylactones, polyacrylamide, Xanthan gum, chitosan, polyethylene oxide,polyvinyl alcohol (PVA), polyvinyl acetate, polyacrylic acid,polyethyleneimine (PEI), sugar alcohols such as sorbitol, sucrose,fructose, lactose, galactose, maltose, erythritol, maltitol, threitol,arabinol, ribitol, mannitol, galactitol, inositol, and xylitol, estersof anhydrosorbitols, secondary alcohol ethoxylates such as TERGITOL,multifunctional alcohols including pentaerytritol, dipentaerythitol,trimethylolpropane, dimethylpropionic acid, and xylonic acid,nucleopbases such as uracil, cytosine, guanine, thymine, andcombinations thereof.

Still other examples include lactic acid, maleic acid, urea, glycolicacid, sorbitol, borax (i.e., sodium borate), proline, a betaine,glycine, histidine, TRIS (tris(hydroxymethyl) aminomethane), dimethylsulfoxide, sulfolane, glycerol, SDS (sodium dodecyl sulfate),dodecylphosphonic acid, or a combination thereof. Of these, certainparticle removal agents may be preferred for use in post-CMP cleaningsteps for microelectronic device substrates, e.g.: maleic acid, borax(i.e., sodium borate), dimethyl sulfoxide, glycerol, or a combinationthereof.

According to certain example cleaning solutions, a total amount of oneor more particle removal agents in a cleaning solution at a point of use(during a post-CMP cleaning process) can be at least about 0.01 weightpercent, more preferably at least about 0.02 weight percent, such as atleast 0.05 weight percent, based on the total weight of the cleaningsolution. Example amounts can be up to about 1 weight percent, morepreferably up to about 0.3 weight percent, e.g., up to about 0.2 weightpercent particle removal agent based on the total weight of the cleaningsolution.

According to certain example cleaning solutions in concentrated form,before dilution to a point of use composition, a total amount of one orparticle removal agents in the cleaning solution concentrate can be atleast about 7 percent, such as at least about 10 weight percent based onthe total weight of the cleaning solution, but not more not more than 20weight percent, preferably not more than 8 weight percent, e.g., notmore than 7 weight percent particle removal agent based on the totalweight of the cleaning solution.

In addition to the particle removal agent, a cleaning composition asdescribed can preferably include one or more other dissolved chemicalingredients that act as cleaning agents to assist in removing residuefrom a surface of a substrate, e.g., during a post-CMP cleaning step.The one or more cleaning agents may act by various known cleaning orsequestration mechanisms, such as by dissolving residue that is anorganic material, by dispersing solid or particulate residue, or byotherwise interacting with or isolating a residue that is present at asurface of a substrate after a CMP step, or that is present in acleaning solution used to clean the substrate during a post-CMP cleaningstep.

Examples of useful organic solvents are known for use in post-CMPcleaning solutions and methods. Example solvents can be polar organicsolvents, alcohols, glycols, and amines, among others. Non-limitingexamples include lower molecular weight alcohols such as C₁ to C₄ alkylalcohols, alkylene glycols, ethanolamines (e.g., monoethanol amine),N,N′-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone,N-ethylpyrrolidone, etc.

Illustrative examples of organic amines include species having thegeneral formula NR¹R²R³, wherein R¹, R² and R³ may be the same as ordifferent from one another and are selected from the group consisting ofhydrogen, straight-chained or branched C₁-C₆ alkyl (e.g., methyl, ethyl,propyl, butyl, pentyl, and hexyl), straight-chained or branched C₁-C₆alcohol (e.g., methanol, ethanol, propanol, butanol, pentanol, andhexanol), and straight chained or branched ethers having the formulaR⁴—O—R⁵, where R⁴ and R⁵ may be the same as or different from oneanother and are selected from the group consisting of C₁-C₆ alkyls asdefined above. When the amine includes the ether component, the aminemay be considered an alkoxyamine. Most preferably, at least one of R¹,R² and R³ is a straight-chained or branched C₁-C₆ alcohol. Examplesinclude, without limitation, alkanolamines such as alkanolamines such asaminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol,dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine,monoethanolamine, triethanolamine, 1-amino-2-propanol,3-amino-1-propanol, diisopropylamine, isopropylamine, 2-amino-1-butanol,isobutanolamine, diisopropanolamine, tris(hydroxymethyl)aminomethane(TRIS), tris(hydroxyethyl)aminomethane, other C₁-C₈ alkanolamines, andcombinations thereof; amines such as triethylenediamine,ethylenediamine, hexamethylenediamine, diethylenetriamine,triethylamine, trimethylamine, and combinations thereof; diglycolamine;morpholine; and combinations of amines and alkanolamines. Preferably,the organic amine comprises monoethanolamine.

Generally, organic solvent can be included in a cleaning solution in anamount that will be useful to be effective in a manner described hereinfor an organic solvent as a cleaning agent, e.g., by dissolving anorganic residue. Particular types and amounts of organic solvent thatare included in a given cleaning solution can be selected based onfactors that include the type of substrate being cleaned, the types andamounts of residue present at the substrate surface, other ingredientsin the cleaning solution, and the conditions (timing, temperature, etc.)used in a post-CMP cleaning process.

According to certain example cleaning solutions, a total amount of oneor more organic solvents in a cleaning solution at a point of use(during a post-CMP cleaning process) can be below about 1 percent byweight based on total weight of the cleaning solution, more preferablybelow about 0.33 weight percent, most preferably not more than 0.13weight percent, e.g., not more than 0.067 weight percent, or not morethan 0.033 weight percent based on the total weight of the cleaningsolution. Preferably, if present, an amount of organic solvent can be atleast 0.0003 weight percent, more preferably at least 0.001 weightpercent, e.g., at least 0.015 or 0.025 weight percent based on the totalweight of the cleaning solution.

According to certain example cleaning solutions in concentrated form,before dilution to a point of use composition, a total amount of one ormore organic solvents in the cleaning solution concentrate can be notmore than 20 weight percent, more preferably not more than 10 weightpercent, most preferably not more than 7 weight percent, e.g., not morethan 2 weight percent, or not more than 1 weight percent based on thetotal weight of the cleaning solution. Preferably, if present, a usefulamount may be at least 0.005 weight percent, more preferably at least0.01 weight percent, such as at least 0.05 weight percent or at least0.2 or 0.35 weight percent based on the total weight of the cleaningsolution.

The cleaning solution can optionally contain at least one chelatingagent. In general, a chelating agent used in a post-CMP cleaningcomposition is a chemical compound that forms a complex molecule,typically with a metal ion, often an iron ion, to inactivate the ionwithin the cleaning solution and prevent chemical reaction or activityby the ion. Various chelating agents are known for use in post-CMPcleaning compositions and can be used in a cleaning composition andmethod of the present description. Certain specific examples includeacid-containing organic molecules, especially carboxylic acid-containingorganic molecules such as linear or branched C₁-C₆ carboxylic acidcompounds that include phthalic acid, succinic acid, citric acid,tartaric acid, malic acid, gluconic acid, aspartic acid, or acombination thereof, as well as, glycine, amino acids and the like.Citric acid can be a preferred chelating agent for chelating iron ions(e.g., Fe⁺², Fe⁺³). Sugar alcohols such as: arabitol, erythritol,glycerol, hydrogenated starch hydrolysates (HSH), isomalt, lactitol,maltitol, mannitol, sorbitol, and xylitol are also preferred chelatingreagents for metal ions.

Other metal chelating reagents contemplated herein include, but are notlimited to, acetic acid, acetone oxime, acrylic acid, adipic acid,alanine, arginine, asparagine, aspartic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid,glutamine, glutaric acid, glyceric acid, glycerol, glycolic acid,glyoxylic acid, histidine, iminodiacetic acid, isophthalic acid,itaconic acid, lactic acid, leucine, lysine, maleic acid, maleicanhydride, malic acid, malonic acid, mandelic acid, 2,4-pentanedione,phenylacetic acid, phenylalanine, phthalic acid, proline, propionicacid, pyrocatecol, pyromellitic acid, quinic acid, serine, sorbitol,succinic acid, tartaric acid, terephthalic acid, trimellitic acid,trimesic acid, tyrosine, valine, xylitol, ethylenediamine, oxalic acid,tannic acid, picolinic acid,1,3-cyclopentanedione, catechol, pyrogallol,resorcinol, hydroquinone, cyanuric acid, barbituric acid,1,2-dimethylbarbituric acid, pyruvic acid, propanethiol, benzohydroxamicacids, tetraethylenepentamine (TEPA), 4-(2-hydroxyethyl)morpholine(HEM), N-aminoethylpiperazine (N-AEP), ethylenediaminetetraacetic acid(EDTA), 1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA),N-(hydroxyethyl)-ethylenediaminetriacetic acid (HEdTA), iminodiaceticacid (IDA), 2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriaceticacid, amino tris(methylene phosphoric acid), hydroxyethylidinediphosphonic acid, ethylenediamino tetrakis (methylene phosphoric acid),ethylenediamino pentakis(methylene phosphoric acid), thiourea,1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, cysteine,glutamic acid, isoleucine, methionine, piperadine, N-(2-aminoethyl)piperadine, pyrrolidine, threonine, tryptophan, salicylic acid,dipicolinic acid, p-toluenesulfonic acid, 5-sulfosalicylic acid, andcombinations thereof.

Other examples of useful chelating agents include carboxylic acidgroup-containing oligomers and polymers derived from monomers that mayinclude one or more of acrylic acid, methacrylic acid, maleic acid,succinic acid, aspartic acid, 2-acrylamido-2-methyl-1-propanesulfonic,acrylamide, phosphonate methacrylamidopropyl trimethylammonium chloride,allyl halide, or a combination thereof. Polyacrylic acid can be apreferred chelating agent for chelating silica nitride (SiN). Stillother examples include: propane-1,2,3-tricarboxylic acid,butane-1,2,3,4-tetracarboxylic acid, pentane-1,2,3,4,5-pentacarboxylicacid, trimellitic acid, trimesinic acid, pyromellitic acid, melliticacid, and combinations of these.

Generally, a chelating agent can be included in a cleaning solution inan amount useful to be effective in a manner described herein for achelating agent. Particular types and amounts of chelating agent thatare included in a given cleaning solution can be selected based onfactors that include the type of substrate being cleaned, the type ofresidue present at the substrate surface, other ingredients in thecleaning solution, and the conditions of a post-CMP cleaning process.

According to certain example cleaning solutions, a total amount of oneor more chelating agents in a cleaning solution at a point of use(during a post-CMP cleaning process) can be up to about 5 weightpercent, such as up to about 2 weight percent, most preferably up toabout 1 weight percent. Preferably, if present, an amount can be atleast 0.0005 weight percent, more preferably at least 0.001 weightpercent, such as at least 0.007 weight percent based on the total weightof the cleaning solution.

According to certain example cleaning solutions in concentrated form,before dilution to a point of use composition, a total amount of one ormore chelating agents in the cleaning solution concentrate can be notmore not more than 20 weight percent, more preferably not more than 13weight percent, most preferably not more than 10 or 7 weight percent,e.g., not more than 3 weight percent, or not more than 1.5 weightpercent based on the total weight of the cleaning solution. Preferably,the amount can be at least 0.008 weight percent, more preferably atleast 0.015 weight percent, such as at least 0.1 weight percent or atleast 0.3 weight percent based on the total weight of the cleaningsolution.

A cleaning solution may optionally contain other ingredients oradjuvants to improve the cleaning effect or efficiency of a post-CMPcleaning step using the cleaning solution. Optionally, for example, acleaning solution may include a pH adjusting agent or buffering systemto control pH of a cleaning solution concentrate or a point of usecomposition. Examples of suitable pH adjusting agents include organicand inorganic acids effective to reduce pH, such as nitric acid,sulfuric acid, phosphoric acid, phthalic acid, citric acid, adipic acid,oxalic acid, methanesulfonic acid, hydrochloric acid, malonic acid,maleic acid, among others. Other option ingredients include a surfactant(any type) or a biocide.

According to the present description, a post-CMP cleaning method asdescribed, which incorporates a cleaning solution that contains particleremoval agent as described, can be useful to clean a substrate after aCMP step, preferably and advantageously in a manner that results in areduced occurrence of brushmarks present at a surface of a substrate atthe end of the post-CMP cleaning step, relative to a comparable cleaningmethod that is performed in an identical fashion (using the samecleaning apparatus, brushes, amount of cleaning solution, cleaning time,cleaning temperature, etc.), on an identical substrate (with comparableresidue), except that the cleaning solution of the comparable cleaningmethod does not contain particle removal agent as described herein(including an amount thereof). According to embodiments of post-CMPsubstrate cleaning methods of the present description, the use acleaning solution as described, which includes particle removal agent(e.g., in an amount as described), can result in a reduced presence ofbrushmarks (especially linear brushmarks) on a surface of a substrate atan end of a post-CMP cleaning process (e.g., by at least 50, 75, 90, or95, or 99 percent) relative to an otherwise identical post-CMP cleaningmethod on an identical substrate (with identical or comparable residue),that uses a cleaning solution that is otherwise identical but does notcontain the particle removal agent.

Also according to the present description, a post-CMP cleaning method asdescribed, which incorporates a cleaning solution as described,containing particle removal agent as described (including an amount asdescribed), can result in a reduced amount of abrasive particles presentat a surface of a polymeric cleaning brush during or at an end of thecleaning step, relative to a comparable cleaning method that isperformed in an identical fashion (using the same cleaning apparatus,brushes, amount of cleaning solution, cleaning time, cleaningtemperature, etc.), on an identical substrate (with comparable residue)except that the cleaning solution of the comparable cleaning method doesnot contain the particle removal agent (e.g., in an amount as describedherein). According to embodiments of post-CMP substrate cleaning methodsof the present description, that use a cleaning solution as described,the presence of abrasive particles present at (e.g., attracted byhydrogen bonding) a surface of a polymeric cleaning brush as described,during or at an end of a post-CMP cleaning process, can be reduced(e.g., by at least 50, 75, 90, or 95, or 99 percent) relative to anotherwise identical post-CMP cleaning method on an identical substrate,that uses a cleaning solution that is otherwise identical but does notcontain the particle removal agent.

Example cleaning solutions are useful for removing residue present at asubstrate surface, or to reduce the presence of (i.e., remove) or reducethe accumulation of abrasive particles at a polymeric surface of acleaning brush. In processing a substrate or a brush for either of thesepurposes, the cleaning solution is not one that is intended to or isused (as described herein) to remove a material that makes up thesurface layer of the substrate. Consequently, a cleaning solution asdescribed does not require and can preferably exclude any substantialamount of chemical material or abrasive material that is useful andintended to have the effect of removing material from a surface of asubstrate, these ingredients including abrasive particles, oxidizer,surfactant, catalyst, etc., of the type that may typically be present ina CMP slurry that is designed to be used in a CMP process to removematerial from a substrate surface.

A cleaning solution as described (in an original form, before being usedin method as described herein) can exclude abrasive particles of a typethat may be present in a CMP processing step. These are solid particles(e.g., nano-particles) present in a CMP slurry for use to mechanicallyremove material from a surface of a substrate during a CMP processingstep. Examples include silica particles, ceria particles, zirconiaparticles, alumina particles, as well as other metal and metal oxideabrasive particles, etc., that exist in solid (non-dissolved) form in aslurry. Cleaning solutions of the present description (in an originalform, before being used in cleaning step) can contain not more than 1,0.1, 0.01, 0.001, 0.0001 weight percent of solid abrasive particlesbased on a total weight of the cleaning solution. These amounts arerepresentative of cleaning solutions at a point of use, and forconcentrate compositions.

Similarly, preferred cleaning solutions as described do not require andcan optionally exclude chemical materials that function by chemicalinteraction with a material that makes up a surface layer of a CMPsubstrate, or with another material of a slurry, to facilitate effectiveremoval of the surface layer material from a substrate surface. Examplesof such chemical materials include surfactant, catalyst (e.g., metal-ioncatalysts, especially iron-ion catalysts), and oxidizer, among others.Example cleaning solutions may contain not more than 1, 0.1, 0.01,0.001, or 0.0001 weight percent of any one or combination of surfactant,catalyst, or oxidizer, based on total weight cleaning solution. Theseamounts are representative of cleaning solutions at a point of use, andfor concentrate compositions.

For purposes of excluding catalyst, oxidizer, and surfactant asingredients from a cleaning solution as described, a “surfactant” is anorganic compound that lowers the surface tension (or interfacialtension) between two liquids or between a liquid and a solid, typicallyan organic amphiphilic compound that contains a hydrophobic group (e.g.,a hydrocarbon (e.g., alkyl) “tail”) and a hydrophilic group. Asurfactant may be of any HLB (hydrophilic-lipophilic balance) value, andmay be charged, uncharged, etc., examples of many varieties ofsurfactants being well known in the chemical and CMP arts.

A “catalyst” is a material that can be effective to provide a metal ionto a solution (e.g., a liquid carrier of a CMP slurry) that, especiallyin the presence of an oxidizing agent, is capable of reversibleoxidation and reduction in the presence of a metal material at a surfacelayer of a CMP substrate, especially a metal material that is beingremoved from the substrate surface during a CMP process step that usesthe slurry, and wherein the metal ion of the catalyst facilitates thatremoval. Examples of metal-ion-type catalysts are well known in the CMParts and can supply a metal ion to the slurry, such as an ion of iron,cobalt, copper, europium, manganese, tungsten, molybdenum, rhenium, oriridium. Examples of such an iron-ion catalysts may be soluble in aliquid carrier and may include ferric (iron III) or ferrous (iron II)compounds such as iron nitrate, iron sulfate, iron halides (includingfluorides, chlorides, bromides, and iodides, as well as perchlorates,perbromates and periodates), and organic iron compounds such as ironacetates, acetylacetonates, citrates, gluconates, malonates, oxalates,phthalates, and succinates, and mixtures thereof.

An oxidizer (a.k.a., oxidizing agents) is a compound that is or includesan inorganic or organic per-compound. A per-compound can be understoodto be a compound that contains at least one peroxy group (—O—O—), or acompound that contains an element in a highest oxidation state. Examplesof compounds that contain at least one peroxy group include hydrogenperoxide and its adducts such as urea hydrogen peroxide andpercarbonates, organic peroxides such as benzoyl peroxide, peraceticacid, and di-t-butyl peroxide, monopersulfates (SO₅ ^(═)), dipersulfates(S₂O₈ ^(═)), and sodium peroxide. Examples of compounds that contain anelement in a highest oxidation state include periodic acid, periodatesalts, perbromic acid, perbromate salts, perchloric acid, perchloratesalts, perboric acid, and perborate salts and permanganates. Anoften-preferred oxidizing agent for CMP slurries is hydrogen peroxide.

At a point of use, a cleaning composition as described and in aconcentrated form can be diluted to form a cleaning solution for use ina post-CMP cleaning step. The concentrate can include chemicalingredients as described in amounts that, upon dilution, will provide apoint of use composition having desired concentrations of eachingredient. The concentrate can have a pH that will be below a pH of ause composition, e.g., a pH of a concentrate may be below 2.5 or below2. The amount of water added to the concentrate to form the usecomposition, i.e., the dilution rate, can be as desired. Exampleconcentrates may be diluted by a factor of 10, 50, 100, or 200, e.g., bycombining a volume of the concentrate with a volume of water that is 10,50, 100, or 200 times the volume of the concentrate.

According to various examples of methods for using a cleaning solutionas described, a microelectronic device substrate can be cleaned in apost-CMP cleaning step, e.g., using a post-CMP cleaning apparatus, toremove residue from a surface of the substrate, including abrasiveparticle residue. The substrate may be a microelectronic devicesubstrate, generally a flat wafer that can include a base, withmaterials that have been selectively deposited onto and selectivelyremoved from the substrate to produce layers of microelectronicfeatures, including a surface layer. The surface layer may be made ofsuch deposited materials, including one or more metal (e.g., copper,tungsten, silver, cobalt, nickel, etc.), insulating or dielectricmaterial (e.g., TEOS, silicon nitride), and semiconducting material. Atthe surface, but not part of a deposited material that makes up thesurface layer of the substrate, residue as described may be present,including abrasive particles that were used in the CMP step.

A specific example of a substrate, with residue, is a post-CMPmicroelectronic device substrate that contains meatal features at asurface (e.g., tungsten, copper, or cobalt as a liner or interconnect(e.g. plug) structure), and one or more non-metal materials such as adielectric material or a barrier layer (e.g., TEOS, silicon nitride,among others). The substrate contains residue at a surface, such asabrasive particles. The abrasive particles may be of any useful type,e.g., alumina, silica, ceria, zirconia, or a related oxide. The abrasiveparticles will generally be of a type that is useful to process thespecific type of wafer and materials at the surface of the wafer. Forexample, a substrate that includes tungsten features and a dielectricmaterial at a surface may be previously processed by a CMP step thatincludes silica abrasive particles.

According to a cleaning step, a CMP substrate having residue at asurface is contacted with a polymeric cleaning brush and cleaningsolution as described is dispensed onto the cleaning brush and substratesurfaces. Relative motion between the brush and the substrate surface,with a desired amount of pressure, is provided. The post-CMP cleaningstep is effective to reduce the amount of residue, including abrasiveparticles present at the substrate surface after the CMP step.

EXAMPLES

Examples illustrating concepts of the invention described herein, aswell as comparative examples are listed in Table 1:

TABLE 1 # Particle Formulation Defects on components, Citric Monoetha-Poly(acrylic Other PETEOS % acid nolamine acid) Sorbitol GlycerolXylitol Arabitol Fructose Mannitol Dextran additives (normalized)Control, 3 4 0.05 0 0 0 0 0 0 0 1 pH 6 Comparative 3 4 0.05 0 0 0 0 0 00 2.8 Sample 1, pH = 2 Sample 1, 3 4 0.05 6 0.54 pH = 2 Sample 2, 3 40.05 3 0.65 pH = 2 Sample 3, 3 4 0.05 6 3 0.22 pH = 2 Sample 4, 3 4 0.056 0.35 pH = 2 Sample 5, 3 4 0.05 6 0.49 pH = 2 Sample 6, 3 4 0.05 6 0.31pH = 2 Sample 7, 3 4 0.05 6 0.28 pH = 2 Sample 8, 3 4 0.05 6 0.25 pH = 2Comparative 3 4 0.05 0 0 0 0 0 0 0 3 2.6 Example Cleaner 1, pH = 2Comparative 3 0 0.05 0 0 0 0 0 0 0 5 5.8 Example Cleaner 2, pH = 2Comparative 3 4 0.05 0 0 0 0 0 0 0 6 3.2 Example Cleaner 3, pH = 2

PETEOS wafers were polished with a colloidal silica based CMP slurry ona IC 1010 pad and cleaned with 5 formulations of different pH's:Control, pH 6, Cleaners 1, 2 and 3 (pH=2) and a commodity, dAmmonia, pH10. Polishing was done on an AMAT Reflexion LK polishing tool, and thedefect inspection was done on a KLAT SP-3 tool, >0.1/0.065/0.060 μmdefect size and a KLAT eDR-7100 defect review tool (microscope, SEM,EDX).

Cleaning was done with Entegris brushes (PVP1ARXR1), with no megasonicstep.

FIG. 1 shows defectivity data on PETEOS wafers cleaned at pH<6 and pH>6,with brush marks detected only when using Cleaners 1, 2 and 3, at pH˜2.

FIG. 2 illustrates the mechanism of brush imprint formation based onsilica-brush hydrogen bonding at low pH.

The brush loading with silica can be also detected using FTIRspectroscopy, where clearly the silica Si—O—Si peak, around 1100 cm⁻¹can be distinguished from the brush characteristic peak, C—O—C, ataround 1016 cm⁻¹ (FIG. 3 ).

A list with H-bonding silica brush cleaning additives used in thisexperiment is presented in Table 2:

TABLE 2 Formulation Additive 1 glycerine + K2S2O5 4 glycerine + formicacid 8 glycerine + 3 MPA 13 glycerine + urea 15 Glycerine + DMSO 16Glycerine + oxalic acid 18 maleic acid 19 glycolic acid 20 sorbitol 21sulfolane

FTIR spectra of silica contaminated brushes cleaned with some of pH 2formulations containing these additives are presented in FIG. 4 :

FIGS. 5 and 6 illustrate defectivity on PETEOS wafers as directcomparison of the Samples 1-8 (Table 1) (current invention, usingenriched silica-H-bonding additives or brush-H-bonding additives) vs.comparative examples without these additives.

1-15. (canceled)
 16. A cleaning solution concentrate useful for cleaninga substrate in a post-chemical-mechanical processing step, the cleaningsolution comprising: cleaning agent, and at least 0.1 weight percentparticle removal agent that includes a hydrogen bonding group.
 17. Theconcentrate of claim 16 comprising: from 0.1 to 20 weight percentcleaning agent, and from 0.1 to 20 weight percent of the particleremoval agent.
 18. The concentrate of claim 16, wherein the cleaningagent comprises one or more of a chelating agent and an organic solvent.19. The concentrate of claim 16, wherein the cleaning agent comprisingcitric acid, monoethanol amine, polyacrylic acid, or a combinationthereof.
 20. The concentrate of claim 16, wherein the cleaning solutionas a pH that is below 2.5.